Anthrapyridone compound and material colored therewith



Patented Jan. 6, 1942 ANTHRAPYRIDONE COMPOUND AND. MATE- RIAL COLORED THEREWITH .Gordon F. Frame, Rochester, N.

Eastman ,Kodak Company, RochesteigN.

Y., assignor to Y., a

corporation of'New Jersey No Drawing. Application September 25,1940, Serial No. 358,285

12 Claims.

This invention relates to new anthrapyridone compounds and their application to the art of coloring. I have discovered that the anthrapyridone compounds, containing a member selected from the group consisting of a phenoxy and a naphthoxy group in the 2-position and a phenylamino group in the 4-position of the anthrapyridone nucleus, constitute a valuable class of compounds. Depending upon their structure, the compounds of my invention possess application for the coloration of organic derivatives of cellulose, silk and wool. Coloration can be effected by dyeing, *printing,. stenciling or like methods. The compounds of my inventionalso appear to stabilize a foam on'theirsolutions and hence probably lower the surface tension of the dye solutions-'a-useful property in the dyeing of I textiles. I

While my invention relates broadly to the dye compounds above defined, it-relates more particularly to the .anthrapyridone compounds having the general formula:

wherein R represents ,a member selected from the group consisting of hydrogen and an alkyl group and R1 and R2 each represents a .phenyl group.

Both sulfonated and non-.sulfonated compounds are included withinthe scope of my invention. The non-sulfonatedcompounds are particularly of value for the dyeing of organic derivatives of cellulose. These non-sulfonated compounds likewise possesssome application for the dyeing of Wool and silk. For the dyeing of organic derivatives of cellulose .such as cellulose acetate silk, non-sulfonated compounds, wherein the group attached to the 2l-position of the anthrapyridone nucleus is a phenoxy nucleus, are generally advantageous.

The nuclear sulfonated compoundsof my invention have little or no utility for the coloration of organic derivatives of cellulose but possess application for the dyeing of wool and silk. Preferably, when the dye compounds of .my invention are to be employed .for the coloration of ganic derivatives of cellulose, further object is to provide coloredtextile maorganicderivatives of cellulose, they should contain no free carboxylic acid group.

It is an objectof myinvention to-provide a new class of anthrapyridone compounds suitable for the coloration of organic derivatives of cellulose, Wool and silk. Another object of my invention is to provide a process for the coloration of orwool and silk. A

terials which are of good fastness to light and washing. Other'objects will hereinafter appear. Typical organic derivatives of cellulose include the hydrolyzed ,as well as the unhydrolyzed cellulose organic acid esters such as cellulose acetate, cellulose formate, cellulose propionateor cellulose butyrate, and the hydrolyzed as well as the unhydrolyzed mixed organic acidresters of cellulose, such ,as cellulose acetate-propionate, cellulose acetate-butyrate, and the cellulose ethers, such as methyl cellulose, ethyl cellulose or benzyl cellulose.

The anthrapyridone compounds of my invention can be prepared by condensing a 2-bromo- 4-phenylamino anthrapyridone or a Z-bromo-- phenylamino N-alkylanthrapyridone with phenols and naphthols. The condensation is effected by heating the anthrapyridone compound with an alkali metalsalt of the phenol or naphthol in the presence of an excess of the phenol or naphthol. 'Where'sulfonated'compounds are desired, the condensation step is followed by sulfonation. The .2 bromo 4 phenylaminoanthrapyridone or the 2-,bromo-4-phenylamino- Nealkylanthrapyridone compounds used as the starting materials can be prepared as described in the prior art. A 2-bromo-4-phenylamino-N- methylanthrapyridone is obtainable, for instance, by the procedure outlined in British Patent .No. 483,325.

It will be understood that the term alkyl as used herein and in thelclaims, unless otherwise indicated, includesrnot only unsubstituted alkyl groups such as the methyl group, the

' ethyl group, a'propyl group or a butyl group but also substituted alkyl groups such as fi-hydroxyethyl, p-hydroxypropyl, p,- -dihydroxypropyl, A-hydroxybutyl, c-ethoxyethyl, A-methoxybutyl, -methoxypropyl, s-chloroethyl, 'y-chloropropyl,

o-hydroethyl, B cya noethyl and 'y-cyanopropyl.

It will be further understood that the terms a phenyl and a naphthyl group, unlessother- "wise indicated, include phenyl and naphthyl groups which are unsubstituted or substituted with substituents such as alkyl, hydroxy,

alkoxy, halogen, sulfo and carboxy,

The following examples illustrate the preparation of the compounds of my invention:

Example 1 stirring at 170180 C. for four'hours under reflux. The product formed is isolated by pouring the reaction mixture into a dilute sodium hydroxide solution sufiicient to dissolve the excess phenol present in the reaction mixture. The desired product remains insoluble and can be collected by filtering following which it is washed with water and dried in a vacuum. The product obtained, N-methyl-2-phenoxy-4-p-toluidinoanthrapyridone, is a blue powder and is free of halogen. It melts at 110-115 C. and dissolves in alcohol with a bluish-red color. 3.7

grams or 90% of the theoretical yield is obtained.

-3.6 grams of the product obtained above is dissolved in a mixture of 18 grams of concentrated sulfuric acid and 25.8 parts of oleum. The solution resulting is stirred at 40 C. for two hours following which the mixture is poured onto ice and the precipitate which is formed is recovered by filtration and washed with a 5% aqueous sodium chloride solution. The precipitate thus obtained is dissolved in a hot dilute sodium hydroxide solution, the solution is filtered and the filtrate treated with a saturated sodium chloride solution. N-methyl- 2-sulfophenoxy 4 sulfo p toluidinoanthrapyridone is precipitated by this treatment and is collected on a filter and dried. It dissolves readily in cold water with a red color.

In this example the preparation of an unsul- .fonated anthrapyridone compound and the corresponding sulfonated anthrapyridone compound is described. The unsulfonated compound colors cellulose acetate silk a bluish-red color while the sulfonated compound colors wool and silk a more reddish color.

Example 2 A mixture of 4 grams of N-Inethyl-2-bromo-4- p-toluidinoanthrapyridone, grams of p-cresol and 6 grams of sodium hydroxide is heated with stirring under reflux for four hours at 170-180 desired product is insoluble and is recovered by filtration, Washed with water, alcohol and ether, and dried. The N-methyl-2-p-cresoxy-4-ptoluidinoanthrapyridone obtained is a bluish-red colored powder dissolving in alcohol with a red color. It does not contain halogen. 3.4 grams or 80.1% of the theoretical yield is obtained. The melting point of the dye is -155 C. By sul- .fonation of the anthrapyridone compound obtained, N-methyl-2-sulfo-p-cresoxy-4-sulfo-p- -toluidinoanthrapyridone can be obtained. Sulfonation and recovery of the dye compound can be carried out in accordance with the general method described in Example 1. The sulfonated dye compound is a reddish-powder which dissolves readily in cold water with a bluish-red color.

By the use of an equivalent gram molecular weight of mand o-cresol for the p-cresol oi the example, N-methyl-2-m-oresoxy-4-p-toluidinoanthrapyridone and N-methyl-2-o-cresoxy- 4-p-toluidinoanthrapyridone, respectively, can be obtained. These compounds can be sulfonated to obtain N-methyl-2-sulfo-m-cresoxy-4-sulfop-toluidinoanthrapyridone and N-methyl-Z-sulfo-o-cresoxy-i-sulfo-p-toluidinoanthrapyridone, respectively.

- Example 3 2.5 grams of N-methyl-2-bromo-4-p-toluidinoanthrapyridone are mixed with 25 grams of pethylphenol and 3.7 grams of sodium hydroxide and the reaction mixture is heated with stirring under reflux at -170 C. for three and onehalf hours. While still warm, the reaction mixture is poured into a dilute sodium hydroxide solution sufiicient to dissolve any free p-ethylphenol and filtered. The product obtained which is N-methyl-2-p ethylphenoxy-4-p-toluidinoan- I, thrapyridone is washed with water and dried.

The product obtained is a reddish-powder which does not contain halogen. It is quite soluble in alcohol, dissolving therein with a red color. 2.3 grams or 84% of the theoretical yield is obtained.

By the substitution of equivalent gram molecular weights of 2-bromo-4-p-toluidinoanthrapyridone, N-fl-methoxyethyl-2-bromo-4-p-toluidinoanthrapyridone, N-ethyl-2-bromo-4-p-toluidinoanthrapyridone and N-methyl-2-bromo- 4-phenylaminoanthrapyridone for the N-methyl- 2-bromo-4-p-toluidinoanthrapyridone of the example, 2-p-ethylphenoxy-4-p-toluidinoanthrapyridone, N-B-methoxyethyl-2-p-ethylphenoxy- 4-p-toluidinoanthrapyridone, N-ethyl-Z-p-ethylphenoxy-4-p-toluldinoanthrapyridone and N- methyl-2-p-ethylphenoxy-4-phenylarninoanthrapyridone, respectively, can be obtained. Similarly, if 2.7 grams of N-p-hydroxyethy1-2-bromo- 4-p-toluidinoanthrapyridone is reacted with 25 grams of p-cresol in accordance with the example, N 3 hydroxyethyl 2 p cresoxy 4-p toluidinoanthrapyridone is obtained.

By sulfonation of the anthrapyridone compounds obtained as described or indicated above, anthrapyridone compounds sulfonated in both the phenyl groups present in the 2- and 4-positions are obtained. Suli'onation and recovery of the dye compounds can be carried out in accordance with the general method described in Example 1. To illustrate, by sulfonation of N'- methyl 2 p-ethylphenoxy- 4 -p-toluidinoanthrapyridone, the sulfonated dye, N-methyl-Z-sulfop-ethylphenoxy- 4 -sulfo p toluidinoanthrapyridone is obtained. This dye is a red powder which dissolves easily in cold water with a bluishred color. The unsulfonated dye colors cellulose acetate silk bluish-red whereas the sulfonated dye colors wool and silk a similar color.

By the use of an equivalent gram molecular weight of m-ethylphenol and o-ethylphenol for p-ethylphenol, anthrapyridone dyes corresponding to those above described but containing an m-ethylphenoxy or o-ethylphenoxy group in the 2-position are obtained. I

Example 4 2.4 grams of N-methyl-2-bromo-4-p-toluidinoanthrapyridone, 24 grams of thymol and 3.5 grams of sodium hydroxide are heated together teenage-r4 withtstirring'at 1160 170 forv 3 hours-$ I, While still warm, the reaction mixture is poured iiito a dilute sodium hydroxide solution sufficient to dissolve any free thymol and filtered. The product obtained, which is N methyl-2-(2'-iso-propyl-5-methyl) -phenorxy-4-p-toluidinoanthrapyridone, is washed.. with water and dried. The

. of'eellulose, swimwear- 'seweufiiimwa.memes;

product obtained does not contain halogen and dissolves in alcohol" with a scarlet color. 1.9 grams or 68.5% of the theoretical yield is obtained. This dye compound colors cellulose acetate silk a scarlet color.

By sulfonationofthe anthrapyridone compound. obtained, my N-methy1-2 Sll1f0r(;2 iSQpl'O- pyl-5' -methyl-) phenox-yrl-sulio-p toluidi'noanthrapyridone can be obtained. Sulfonation and recovery of the dye compound can be carried out in accordance with the general proceduredescribed in Example 1. The sulfonated dye compound is red and dissolves in-water with a scarlet color. It colors wool and silk scarlet.

Example 5 i A mixture of 2.5 gramslof N-methyl-2-bromo- 4-p-toluidinoanthrapyridone; grams of 5- naphthol and 3.7 grams of sodium hydroxide is heated withstirring under reflux for 3 /2 hours at 160-170" Ci" While"sti1l{warm, the reactionfmixture is poured "'intofadilute sodium hydroxide and filtered. The productbbtained, which is N-methyl-2-p-naphthoxy 1- 4 p t'oluidin'oanthrapyridon'e, is washed with" Watel"a1l'd dried; The dye product is free from halogen andissoluble in alcohol dissolving therein with a yellowishred color. This dye compound colors cellulose acetate silk yellowish-red.

By sulfonation of the anthrapyridone compound obtained, N-methyl-"2-sulfo-fl-naphthoxy- 4-sulfo-p-toluidinoanthrapyridone can be obtained. Sulfonation and recovery of the dye compound can be carried out in accordance with the general method described in Example 1. The sulfonated dye compound dissolves in cold water with a brownish-red color and colors Wool and silk a similarcolor.

,-N=l w dihydroxypropyl 2-bromo-4 p tolu'idino anthrapyridona N-B-sulfoethyl-2-bromo 4 110111 idino anthrapyridone, 2-bromo-4-p -toluidin'o an thrapyridone and N-methyl-2-bromo=4 -o-toluidinov anthrapyri'done, 'for: example; can be sub"- stituted for the anthrapyridone compoundof'the example to obtain corresponding anthrapyridone compounds wherein the bromine atom in the 2- position is replaced by pT-naphthol. These compounds can be sulfonated to yield the corresponding sulfonated dyes. By the substitution of an equivalent gram-molecular weight of a-naphthol for B-naphthoLi the corresponding unsul-" ionated and sulfonated: anthrapyridone compounds can be obtained; that is," the fl-naphthol group is replaced by .m-naphthol.

It will be understood that the examples are intended to be "illustrative=- and not limitativ'e" of my-dnventi'on as numerousather anthrapyridone compounds included "within the scope of my*in'= vention can be prepared. The unsulfonated compounds color'organic derivatives of cellulose, such as cellulose acetate silk, the colors indicated in the examples. The sulfonated compounds color wool and silk substantially the same color as the corresponding unsulfonated compounds colorcellulose acetate silk.

The compounds of my invention can be employed for the coloration of organic derivatives employed for coloring these materialsfi fil -the case of wool and silk the dye can be dissolved in water, the material added and dyeing carried out at, a temperature Of'lO -85" C. untilcomplete. For the dyeing-of cellulose acetate silk,

the dye can be ground tota fine powder, intimately mixed witna/solubilizing or dispersing agent such as soap or alsulfonated oil such as sulfonated castor oiL'andFadded to water to form a dyebath. Followingthis; the dyebath can be heated to 3035-C.,' the cellulose acetate material to be dyed added, the temperature of the dyebath" raised {to} "%85 C. and maintained at this temperature untildyeing? is-c'o'mplete: The amount of'dye'td e fem lp ed yarns, depending upori thed'epthof hade'fdesir'edi ilnioii'nts r"ang in'g froinl t63%'"by'weighti"based"orr'th Weight of the-cloth, are ordinarily employed.

I claim:

1. Anthrapyridone, compounds selected from the group consisting of 'sulfonated and unsulfonated anthrapyridone compounds containing a member selected from thelgroup consisting of hydrogen andan alkylgroup'--in'the l-position, a

member selected from the group consisting ofconsisting of a phenoxy and a naphthoxy ygroup' in the 2-position and a phenylamino group inthe 4-position of the anthrapyridone nucleus, said anthrapyridone compounds containingno other substituents in addition to those specified above. 3. An anthrapyridone compound having the formula:

x x g.

wherein R1 represents a nieniber slected frbm the'group consisting of hydrogen and arfalkyl group, R1 represents a member selected from the group consisting of a phenyl and a naphthyl group and Rz-represents a phenyl group.

4. An anthrapyridone'"compound having the formula: m s

wherein. R represents a member selected from the group consisting of hydrogen and an alkyl group and R1 and R2 each represents a phenyl group.

;5. An anth-rapyridonecompound having the iormulapq v,

U u HNR1 v wherein R represents a member selected from the group consisting of hydrogen and an alkyl group'and R1 and R2 each represents a phenyl group, substituted with at least one alkyl group. 6. An anthrap'yridone compound having the formula:

wherein .X and X1 each represents a member selected from the group consisting of hydrogen and an alkyl group and n stands for a small whole positive number.

7. An anthrapyridone compound having the 5 formula:

wherein X and X1 each represents a member selected from the group consisting of hydrogen and an alkyl group and n stands for a small whole positive number.

8. The anthrapyridone compound having the formula: V

I '9. The anthrapyridone compound having the formula:

10. Textile-material colored with an anthrapyridone compound having th formula:

wherein R represents a member selected from the group consisting of hydrogen and an alkyl group and R1 and R2 each represents a phenyl group.

12. A cellulose acetate colored with a nonsulfonated anthrapyridone compound having the general formula:

l? O BIN-11:

wherein R represents a member selected from the group consisting of hydrogen and an alkyl group and R1 and R2 each represents a. phenyl group.

GORDON F. FRAME. 

